Herbicidal compositions containing various benzylthiodiazoles and triazines

ABSTRACT

Herbicidal compositions comprise a compound of the formula   WHEREIN R1 is hydrogen or alkyl, X is oxygen or sulfur, Y1 is halogen, lower alkyl, lower alkoxy or nitro, and k is zero or an integer from 1 to 5, or such compound in combination with one or more of salt or ester thereof which is represented by the general formula:   WHEREIN A is lower alkylene, Y2 is chlorine or methyl, M is hydrogen, alkali metal, lower alkyl or lower alkenyl, and m is zero or an integer from 1 to 5; a 3,4-dichloroanilide which is represented by the general formula:   WHEREIN R2 and R3 respectively are hydrogen or lower alkyl; a 1,3,5-triazine compound which is represented by the general formula:   WHEREIN Y3 is chlorine or lower alkylthio, R4 is lower alkyl, and R5 is azido or lower alkylamino, or a phenylurea compound which is represented by the general formula:   WHEREIN Y4 is halogen or halogen-substituted lower alkyl, R6 and R7 respectively are lower alkyl or lower alkoxy, and n is zero, 1 or 2.

llnite tates llagimoto et al.

[ Jan. 22, 1974 HEIRBIICIIDAL COMPOSITIONS CONTAINING vnmous BENZYLTlHlODlAZOLES AND TRIIAZINIES [75] Inventors: Hiroshi l-llagimoto; Toshiharu Arai;

Harutoshi Yoshikawa; Mitsuo Watanabe, all of Kyoto; Yoshiyuiri Okada, Osaka, all of Japan [73] Assignee: Takeda Chemical Industries, Ltd.,

Osaka, Japan [22] Filed: Mar. 31, 1970 [21] Appl. No.: 24,386

[30] Foreign Application Priority Data Primary Examiner-Lewis Gotts Assistant ExaminerCatherine L. Mills Attorney, Agent, or Firm-Wenderoth, Lind and Ponack ABSTRACT Herbicidal compositions comprise a compound of the formula wherein R is hydrogen or alkyl, X is oxygen or sulfur, Y is halogen, lower alkyl, lower alkoxy or nitro, and k is zero or an integer from 1 to 5, or such compound in combination with one or more of salt or ester thereof which is represented by the general formula:

wherein A is lower alkylene, Y is chlorine or methyl, M is hydrogen, alkali metal, lower alkyl or lower alkenyl, and m is zero or an integer from 1 to 5; a 3,4- dichloroanilide which is represented by the general formula:

COR

wherein R and R respectively are hydrogen or lower alkyl; a 1,3,5-triazine compound which is represented by the general formula:

Ya l

wherein Y is chlorine or lower alkylthio, R is lower alkyl, and R is azido or lower alkylamino, or a phenylurea compound which is represented by the general formula:

wherein Y is halogen or halogen-substituted lower alkyl, R and R respectively are lower alkyl or lower alkoxy, and n is zero, 1 or 2.

4 Claims, No Drawings This invention relates to new herbicides. More particularly, the invention relates to herbicides containing one or more of 2-benzylthiol ,3,4-oxa(or thia) diazoles represented by the general formula:

wherein R is hydrogen or alkyl, X is oxygen or sulfur, Y is halogen, lower alkyl, lower alkoxy or nitro, and k is zero or an integer from 1 to 5.

It has unexpectedly been discovered that 2- benzylthio-l,3,4-oxa (or thia)diazole compounds of the general formula (I) are capable of destroying both dicotyledonous and monocotyledonous weeds without causing any injurious effect upon a wide range of crops such as paddy rice plants, corn, soy beans, ground nuts, radish, eggplants, sugar beats, tomatoes and carrots and that they are particularly phytotoxic to such monocotyledonous weeds as Echinochloa crusgalli (l...) Beauv., Digitaria adscendens Henr., Cyperus difformis L., Eleocharis acicularis Roem. et Schult. and Avena fatua L.

It has also been discovered that when a compound represented by the formula (I) is used as herbicide in combination with one or more of a phenoxy-fatty acid or salt or ester thereof which is represented by the general formula:

COR 1 wherein R and R respectively are hydrogen or lower alkyl; a 1,3,5-triazine compound which is represented by the general formula:

'Yli

wherein Y is chlorine or lower alkylthio, R is lower 6 alkyl, and R is azido or lower alkylamino, or a phenylurea compound which is represented by the general formula:

wherein Y is halogen or halogen-substituted lower a1- kyl, R and R respectively are lower alkyl or lower alkoxy, and n is zero, 1 or 2, each of the compounds (II), (III), (IV), (V), acts as a strong synergist for the compounds (I), the resulting herbicidal efi'ect being of the respective compounds.

As regards the above-mentioned formulas (l) to (V), alkyl represented by R is exemplified by methyl, ethyl,

n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, namyl, n-hexyl, n-heptyl, n-octyl, nnonyl and the like, lower alkyl represented by M, Y, R, R R, R and R is exemplified by methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, sec.-butyl, n-amyl, isoamyl and the like, halogen represented by Y and Y is exemplified by chlorine, bromine, fluorine and the like, lower alkoxy represented by Y, R and R is exemplified by methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, isopentoxy and the like, lower alkylene represented by A is exemplified by methylene, ethylene, propylene, lmethylethylene, butylene, l-methylpropylene, 2- methylpropylene, l-ethylethylene, pentylene and the like, lower alkylamino represented by R is exemplified by methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec.- butylamino, tert.-butylamino, n-pentylamino, isopentylamino and the like, lower alkylthio represented by Y is exemplified by methylthio, ethylthio, n -propylthio, isopropylthio, n-butylthio, isobutylthio, sec.- butylthio, tert.-butylthio, n-amylthio, isoamylthio and the like, halogen substituted lower alkyl represented by Y is exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-amyl, isoamyl, substituted by one or more halogen atom, e.g., chlorine, bromine and fluorine, alkali metal represented by M is exemplified by sodium, potassium and the like, and lower alkenyl represented by M is exemplified by vinyl, allyl, l-butenyl, Z-butenyl, 3-butenyl and the like.

Some of the 2-benzylthio-l,3,4-oxa(or thia)diazoles represented by the general formula (I), accompanied by their melting points (mp) or boiling points (bp), are shown below.

1. 2-(benzylthio)-5-methyl-1,3,4-0xadiazole, bp

2. 2-( 2-chlorobenzylthio)-5-methyl-l ,3,4-

oxadiazole, bp l58-l59 C. 3. 2-( 2,4-dichlorobenzylthio)-5-methyl-l ,3 ,4-

To 4.3 parts by weight of 2-(n-propyl)-A -l,3,4- oxadiazoline-S-thidn dissolved in 50 parts by volume of ethanol is added 1.2 part by weight of sodium hydroxide dissolved in 5 parts by volume of water, followed by the addition of 4.8 parts by weight of o-chlorobenzyl chloride. The mixture is heated at 7080 C on a water bath for 2 hours. Sodium chloride precipitated is filtered off and ethanol is distilled off from mother liquid, whereby an oily substance is obtained. The oily substance is dissolved in 50 parts by volume of benzene and then washed with water. After elimination of the benzene by means of distillation, the residue is distilled under reduced pressure to give 7.0 parts by weight of 2-( 2-chlorobenzylthio)-5-(n-propyl)- l ,3,4-oxadiazole which is pale-yellowish oily substance. pu 164I69 C.

The following are typical compounds of the general formula (II):

A. 2,4-dichlorophenoxyacetic acid ethyl ester B. 2-methyl-4-chlorophenoxyacetic acid ethyl etser C. 2-methyl-4-chlorophenoxyacetic acid allyl ester D. a-(2-methyl-4-chlorophenoxy)-propionic acid E. 2,4,S-trichlorophenoxyacetic acid ethyl ester F. 2,4-dichlorophenoxybutyric acid ethyl ester The following are typical compounds represented by the above general formula (III):

A. 3,4-dichloropropionanilide B. N-methyl-3,4-dichloropropionanilide C. 3 ,4-dichloroacetanilide D. N-methyl-3,4-dichloroacetanilide E. N-ethyl-3,4-dichloropropionanilide The following are typical compounds of general for mula (IV):

a. 2-chloro-4,6-bis(ethylamino)-1,3 ,S-triazine b.

2-chloro-4-ethylamino-6-isopropylamino-1,3,5- triazine c. 2-cl1loro-4,6-bis(isopropylamino)-l,3,5-triazine d. 2-methylthio-4,6-bis(ethylamino)- l ,3,5-triazine e. 2-methylthio-4,6-bis(isopropylamino)- l ,3,5-

triazine f. 2-methylthio-4-methylamino-6-isopropylamino- 1,3,5-triazine g. 2-methylthio-4-ethylamino-G-isopropylamino- 1,3,5-triazine 2-methylthio-4-azido-6-( l-cyanomethylethylamino)-1 ,3 ,S-triazine The following are typical compounds of general formula (V):

a. 3-phenyl-l 1 -dimethylurea b. 3-(4chlorophenyl)-1,l-dimethylurea c. 3-( 3,4-dibromophenyl )-l ,l-dimethylurea d. 3-( 3 ,4-dichlorophenyl)- l l -dimethylurea e. 3-( 3-trifluoromethylphenyl)-1 l -dimethylurea f 3-(4-chlorophenyl)- 1 -methyl' 1 -methoxyurea g. 3-( 3 ,4-dichlorophenyl 1 -methyl- 1 -methoxyurea h 3-( 4-bromophenyl 1 -methyl- 1 -methoxyurea i. 3-( 3-chIoro-4-bromophenyl)- 1 -methyl- 1 methoxyurea j. 3-( 3-trifluoromethylphenyl)- 1 -methyl- 1 methoxyurea k. 3-(3,4-dichlorophenyl)-1-methyl-l-butylurea When a compound represented by the formula (I) is used as herbicides in combination with one or more of the compounds represented by the formula (II), (III), (IV) and (V), the preferred ratios of a compound (I) to one or more of the compounds (II), (III), (IV) and (V) is l: 0.1 1.0.

Broadly speaking, the compounds used in this invention are herbicidically effective and are employed at levels of from about 1 kg per hectare to about 10 kgs per hectare for general weed control. For selective weed control in crops, rates of 2 kgs per hectare to 6 kgs per hectare will generally be used and in preemergence treatments 1 kg per hectare to 5 kgs per hectare may for example be used.

To put the herbicides of this invention to use, the composition is first diluted to a suitable concentration and applied either to the soil as a pre-emergence herbicide or to the standing weeds for post-emergence treatments. To control hydrophytes, the composition may be applied either directly to the weeds or to the water where the weeds grow, or to both. When directly applied to weeds, the composition according to this invention acts as a powerful contact poison to suppress growth of the weed or completely destroy the weed. Even when the herbicidal composition is applied to the locus of the weed, not in direct contact therewith, the weed suffers from a considerable decay or growth suppression. Furthermore, in so far as it is properly used, the compositions according to this invention exhibit excellent selectivity.

Depending upon the purpose of application, the herbicides of this invention can be applied in various manners. Thus, one or more of the 2-benzylthio-l,3,4- oxa(thia)diazoles of the general formula (I), which may be mixed with a member selected from the group consisting of phenoxy fatty acid compounds represented by the general formula (II), 3,4-dichloroanilide compounds represented by the general formula (III), 1,3,5-triazine compounds represented by the general formula (IV) and phenylurea compounds represented by the general formula (V) and a mixture thereof, is directly applied as such or used otherwise. The above compounds are dissolved or dispersed in a suitable liquid vehicle (e.g., solvent) or mixed with a suitable ointment base or solid carrier (e.g., diluent or filler) or absorbed thereon, with or without the addition of an emulsifier, dispersing agent, suspension aid, extender, penetrating agent, wetting agent, thickner, stabilizer and the like, and the resulting oil solution, emulsion, wettable powder, dust, tablet, granule, aerosol or ointment, for instance, may be applied.

The proper proportion of the effective ingredients in the herbicide, though it depends upon the purpose in application, lies somewhere between about 1 to about percent for such preparations as emulsifiable solutions and wettable powders, and between about 0.1 to about 10 percent for oil, dusts and other forms. Those concentration ranges may be somewhat modified to suit the purpose of application. Regarding the emulsions, wettable powders and some other forms, they are preferably diluted with water, for instance, to a suitable concentration (e.g., 1,000 10,000 times) before application.

The solvents which can be used in the composition of this invention include, among others, water, various alcohols (e.g., methanol, ethanol, ethylene glycol, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), ethers (e.g., dioxane, tetrahydrofuran, cellosolve, etc.), aliphatic hydrocarbons (e.g., gasoline, kerosene, fuel oil, machine oil, etc.). aromatic hydrocarbons (e.g., benzene toluene, xylene, solvent naphtha, methyl naphthalene, etc.), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, etc.) acid amides (e.g., dimethylformarnide etc.), esters (e.g., ethyl acetate, butyl acetate, glycerin fatty acid esters, etc.), nitriles cides, natural insecticides, etc.), ascaricides, synergists,

attractants, repellents, perfumes and fertilizers.

The following experimental data are given to illustrate the weed control effects of the herbicidal compo- (e. g., acetonitrile etc.) and the like. Those solvents may Sltions of this invention. be employed either singly or in combination. In the following description, the Compounds The aforesaid diluent or filler means any of such maand correspond to the aforementioned terials as vegetable powders (e.g., soybean powder, tocompounds and respectively, bacco leaf powder, wheat flour, saw dust, etc.), mineral and the Compounds powders (e.g., kaoline, bentonite, clay, pyrophyllite w and powder and other tales, diatomite, mica powder and mean the Compounds enumerated under other siliceous materials), alumina, sulfur powder, actilike numerals in the llstlngs of the Compounds vated carbon and the like. Those materials may be used and respeetlvely' lt is also Understood i h i l or i bi i that g/A means the number of grams of each test com- The ointment base may be chosen from among poly- Pound P acreethylene glycol, pectin, glyceryl monostearate and other polyhydric alcohol esters of higher fatty acids, EXPERIMENT various cellulose derivatives such as methyl cellulose y p with 12 em diameter were sown wlth 100 etc., sodium alginate, bentonite, higher alcohols, poly- Seeds of Oryza saliva Echinochloa er -8 hydric alcohols, e.g., glycerine, vaseline, white vase- Beauvoryzicola Ohwl, Ludwiglh Proslmra line, liquid paraffin, lard, various vegetable oils, lano- Roxb Digitaria adscendens and Amaranthus lin, lanolin anhydricum, hydrogenated oil, waxes and fl respectively, and the emerged Seedlings were various resins. Those materials may be employed either thinned to leave 10 Plants each The herbicidal P singly or in combination and with or without the addiratlons were applied at the Second or thlrd leaf Stage of tion of surfactants and other additives. h plant- The P y Solution was P p y Regarding the surfactants which can be used as the Solving predetermmed amounts (g/A) of compollllds aforesaid emulsifier, extender, penetrating agent, dis- (1) m 50 each f acetone followed by the addlilon persing agent, etc., use can be made, as required, of a of polyoxysorbltan mqnolaurate to each 9 wide variety of surface active agents, inclusive of soaps, wh'ch.was then made. up with water to tptal quantity higher alkyl sulfates alkyLsult-onates, alkylaryb of l0litres. (The Echmochloa and Ludwigia were cultisulfonates, quaternary ammonium salts, oxyalkylavated under 1 cm.deep water whlle Dlgltana mines, polyalkylene-oxide and anhydrosorbitol surfacklmhus were culnvated under .P field. commons) tants, etc. For the same purpose, it is also possible to fter i degree of m-lury e by each employ, as required, such other materials as casein, gelplant a mvesugatefl T degree s mlury are atin, starch, alginic acid, agar, polyvinyl alcohol, carpressed m the following mdlces of Injury boxymethyl cellulose, terpene oil, rice bran oil, benton- INDICES OF INJURY ,iteenq. @119. i e. o; No injury at all The compositions which can thus be obtained may be 1: Slight injury (Fresh weight did not decrease to further mixed with other herbicides, plant growth regumore than percent of the control) lators such as various germicides (e.g., copper germi- 2: Severe injury (Fresh weight decreased to less than cides, organic chlorine germicides, organic sulfur ger- 60 percent of the control) micides, phenolic germicides, etc.), insecticides (or- 3: Complete decay ganic chlorine insecticides, o rganic phosphorus insecti- The results are set forth in Table 1.

Table l (Post-emergence treatment) Compound (I) No. Dosage (g/A) Transplanted rice Echinochloa Ludwigia Digitaria Amaranthus (l) 50 0 2 l 2 1 l 3 2 3 3 (7) 50 0 2 l 2 2 I00 I 3 2 3 3 (8) 50 O 2 l 2 l 100 l 3 2 3 2 (9) 50 O 2 l 2 l 100 l 3 2 3 2 (10) 50 0 l l l l 100 l 2 2 2 2 (l l) 50 0 2 l 2 l 100 l 3 2 3 2 Table l Cor1tin11ed (Post-emergence treatment) Compound (I) No. Dosage (g/A) Transplanted rice Echinochloa Ludwigia Digitaria Amuranthus 14 o 1 1 2 2 2 100 2 2 3 3 3 (I5) 50 l 2 2 2 l 100 2 3 3 3 3 (16) so 0 2 2 2 2 100 l 3 3 3 3 17 50 0 1 1 2 1 I00 0 3 2 3 2 (i8) 50 0 I l 2 1 I00 0 3 2 3 2 19 50 0 2 2 3 1 2 100 1 3 3 3 3 (20) 50 0 2 1 3 2 100 l 3 2 3 3 (21) 5O 0 3 l 2 l 100 l 3 3 3 2 (22) 50 0 2 l 2 l 100 l 3 2 3 2 23 so 0 2 1 2 1 100 l 3 2 3 2 24 I 50 0 3 2 3 2 100 2 3 3 3 3 (25) 50 0 3 2 3 3 100 l 3 3 3 3 (26) 50 0 2 l 2 l 100 l 3 2 3 2 (27) 50 l 2 l 2 1 I00 2 3 2 3 2 (28) 5O 1 2 l 2 1 I00 2 3 2 3 2 29) 50 1 3 2 3 1 100 2 3 3 3 2 (30) 50 l 2 l 2 1 I00 2 3 2 3 2 (31) 50 l 3 2 3 2 100 2 3 3 3 3 (32) 50 l 2 l 2 l 100 2 3 2 3 2 (33) 50 1 1 O l 0 100 2 3 2 2 l (34) 50 l l 0 2 l 100 2 3 2 2 2 (35) 50 1 2 0 2 1 I00 2 3 2 3 2 (36) 50 1 l 0 l 0 100 l 2 l 3 2 (37) 50 0 0 0 l 0 100 l 2 2 2 1 (38) 50 l 2 l 2 1 I00 2 3 2 3 2 (39) 5O 0 2 2 2 2 100 1 3 3 3 3 (40) l 2 2 2 2 2 3 3 3 3 (41) so 0 2 1 2 2 100 2 3 3 3 3 42 50 o 1 1 2 2 100 1 2 2 3 3 (43) 50 l l l l 2 100 2 3 3 2 3 50 0 l l 2 1 100 l 2 2 3 2 4s 50 1 1 1 l 3 100 2 2 2 2 3 (46) 50 0 0 1 1 1 100 0 2 2 2 2 (47) 50 0 2 1 1 1 100 0 3 2 2 2 4s 50 0 2 1 2 2 100 1 3 2 3 3 (49) 50 0 2 0 2 2 100 0 3 3 3 3 (50) 50 0 l l 2 1 100 l 2 2 3 2 (51) 50 O l 0 2 2 100 0 2 2 3 3 (52) S0 0 2 O 2 2 I00 0 3 2 3 3 (53) 50 0 1 l 2 2 100 0 3 3 3 3 54 so 0 0 0 0 1 I00 0 l 2 2 3 EXPERIMENT 2 Roxb., Digltaria adscendens Henr. and Amaranthus re- Clay pots with 12 cm diameter were sown with rice, fl respectively, 100 Seeds of each Plant P Echinochloa crus-galli (L.) Beauv., Ludwigia prostrata pot, and the spray solutions were sprayed evenly over 1 1 12 the S011 surfaces. The herblcidal preparat1ons were 20 days, the degree of lnjury sustained by each plant made as per the procedure of Experiment 1, and folwas investlgeted. lowlng the applicanon, the plants were cultlvated under The degrees of in ury were evaluated by the standard the same conditions as Experiment 1 for 20 days. After given 1n Expenment 1.

TABLE 2 Compound (I) No. Dosage (g/A) Transplanted rice Echinochloa Ludwigia Digitaria Amaranthus 1 50 1 2 1 2 1 100 3 3 2 3 2 2) 50 2 3 2 1 2 100 3 3 3 3 3 3) so 2 3 3 3 3 100 3 3 3 3 3 4 50 2 2 1 2 3 100 3 3 2 3 3 5 50 2 3 3 2 2 100 3 3 3 3 3 (6) 50 2 2 2 2 2 100 3 3 3 3 3 (7) 50 1 2 2 2 2 100 2 3 3 3 3 (a so 1 2 1 2 1 100 2 3 2 3 2 9 50 1 3 3 2 1 100 2 3 3 3 2 10 50 1 3 3 2 1 100 2 3 3 3 2 11 50 1 3 2 2 1 100 2 3 3 3 2 (12) 50 1 3 1 2 2 100 2 3 2 3 3 13 50 2 2 1 2 1 100 3 3 2 3 2 14 so 1 2 2 2 1 100 2 3 3 3 2 (15 50 1 3 3 3 2 100 2 3 3 3 3 (I6) 50 1 3 3 3 3 100 2 3 3 3 3 (17) so 0 2 1 2 1 100 0 3 2 3 2 (I8) 50 0 3 3 3 3 100 0 3 3 3 3 19) 50 0 2 1 2 1 100 0 3 2 3 2 (20) so 0 2 1 2 2 100 1 3 2 3 3 (21) 50 0 3 2 3 3 100 1 3 3 3 3 (22) 50 0 3 2 3 2 100 1 3 3 3 3 (23) 50 0 2 l 2 l 100 1 3 2 3 2 (24) 50 l 3 3 3 2 100 2 3 3 3 3 2s) 50 o 3 3 3 2 100 1 3 3 3 3 (26) 50 0 3 1 2 1 100 1 3 2 3 2 (27) 50 1 3 1 2 1 100 2 3 2 3 2 (28) so 1 2 1 1 1 100 2 3 2 3 2 (29) 50 1 2 1 1 1 100 2 3 2 3 2 (30) 50 1 3 3 2 2 100 2 3 3 3 3 (31) so 1 3 3 2 2 100 2 3 3 3 3 (32) 50 1 2 2 2 1 I00 2 3 3 3 2 (33) 50 3 3 0 1 1 100 3 3 2 3 3 (34) 50 1 1 0 0 0 100 2 3 2 2 1 (3s) 50 3 3 2 2 0 100 3 3 3 3 2 (36) 50 l 2 2 1 2 100 2 3 3 3 3 37 50 3 3 3 2 0 100 3 3 3 3 2 (38) 50 2 3 2 2 1 100 3 3 3 3 2 39) 50 1 3 2 2 2 100 2 3 3 3 3 40 2 3 3 2 2 3 3 3 3 3 (41) 50 3 2 3 0 1 100 3 3 3 2 3 (42) 50 3 3 0 2 o 100 3 3 2 3 2 43) 50 2 3 2 0 0 TABLE 2 -Continued Compound (I) No. Dosage (g/A) Transplanted rice Echinochloa Ludwigia Digitaria Amaranthus 100 3 3 3 2 l 44 so 3 3 3 2 0 100 3 3 3 3 2 (45) 50 3 3 2 l 0 100 3 3 3 2 2 (46) 5O 3 3 2 l 2 I00 3 3 3 3 3 (47) SO 2 3 2 1 0 100 3 3 3 2 2 (48) 5O 2 2 3 0 1 I00 3 3 3 2 2 (49) 50 3 2 3 0 O 100 3 3 3 2 2 (50) 50 2 3 2 l 0 100 3 3 3 3 2 s 1 so 2 2 0 l o 100 3 3 2 3 l (52) 50 2 3 2 0 0 100 3 3 3 2 2 s3 50 1 1 2 o 0 100 2 3 3 2 l (54) 50 O 0 2 0 0 100 l 2 2 l l EXPERIMENT 3 10 day after sowing or transplanting, each pot was irril/2,000-Are Wagners pots were planted with rice plants with four-five leaves (variety: Manryo), six plants to each pot. Each of those same wahisb 25 sown with Echinochloa crus -gqlli, Cyperus cm-rhizome of Eleo cha ris aci'cu laris Roem, et Sch ult. In

gated to a constant water depth of 3 cm, and granules composed of 3 percent compound (I) 0.7 percent compound (II) and the balance of bentonite were uniformly applied to the water in each pot at the rate of 300 g/are. 20 days after the application of the granules, the herbicidal activity of these granules were measured. The results are set forth in Table 3.

TABLE 3 Compound (I) No.

Compound (II) No.

Transplanted rice Echinochloa Cyperus Monochoria Eleocharis EXPERIMENT 4 Digitaria adscendens Henr. [plant( 10-20 cm high)], Setaria viridis Beauvois (15-20 cm), Polygonum blumei Meisner (stem height 35-40 cm), and Chenopodium amount to be contained is 48g/are, respectively, while both compounds are used as the active ingredients, the respective amounts of compounds (I) and compound (III) to be contained are 40g/are and 8g/are) were apalbum cemforubnfm Makmo (Stenl helgh: plied to the entire fohages of the plants (2 replicates). 35-40 cm) were cult1vated 1n concrete pots w1th l m 3 weeks after the treatment, top fresh weight of each 1n area, and the spray solutions prepared by the s1m1lar w d h d d h manner as Experiment 1 employing the compound (I) ee was welg e an t e average of two rephcates and/or (III) as active ingredient(s) (when the comwas taken: pound (I) or (III) 18 the sole active 1ngred1ent, Its The results are set forth in Table 4.

Table 4 C d Fresh weight (I) No. (III) No. Digitaria Fresh weight Setaria Fresh weight Polygonum Fresh Chenopodium Fresh eight (K/POU (8/9 Weigh! (8/9 0 (811 1 164 124 296 492 2 110 108 220 447 3 98 85 218 386 13 171 131 305 483 39 167 115 343 470 4 178 128 350 485 4 159 110 308 466 5 177 122 377 498 (A) 70 66 77 101 13' 125 111 I96 294 1 (A) 14 0 48 77 1 13' 23 26 171 I98 2 (A') 6 0 0 48 3 (13') 19 133 138 13 (A') 24 25 38 87 39 13' 21 18 115 109 43 (A') 17 19 28 53 46 (A') 18 22 47 4 13' 43 42 132 177 53 (A') 31 26 55 175 134 375 493 EXPERIMENT 5 l/5,000-Are Wagner's pots were sown with Echinochloa crus-galli Beauv. var. oryzicola Ohwi, 30

' seeds per pot, and the plants were cultivated under the and Potamogeton distinctus A. Benn. were transplanted to pots, one species to each pot and five rhizomes per pot. Under a 3 cm-deep cover of water, the plants were cultivated until the plant heights of Eleochalis, Cyperus and Potamogeton reached 3 cm (spread all over the pot), 10 cm and 15 cm, respectively. Further separately, rice was transplanted to pots at the rate of six applied to the weeds under submerged conditions, at the rate of 300 g. granules per are. The granules contained 4 percent of a compound (I) and l percent of a compound (IV) or a compound (V) or 4 percent of compound (I) or 1 percent of a compound (IV) or (V), separately, with bentonite making up for the balance in each instance. 4 weeks after application of the granules, top fresh weight of each surviving weed was weighed alive and the herbicidal activity of each granular composition was calculated by means of the following equation. The experimental design comprised three replicates.

Rate of inhibition 150 plants per pot. When the weeds reached those prede- [1 (Fresh weght of treated plant/Fresh s of termined growing stages and 10 days after the transcontrol planolx 100 (pemem) plantation of rice, the granules prepared below were The results are set forth in Table 5.

TABLE 5 Rate of inhibition ('36) Compound (I) No. Compound (IV) Transplanted rice Echinochloa Eleocharis Cyperus Potamogeton No. or (V) No.

12) o 22 15 o 0 14 0 39 23 0 7 (15) 0 37 35 3 4 0 18 30 0 o (18 0 25 19 4 6 (19 0 29 18 7 5 (23) 0 20 11 7 8 (35) 0 34 22 3 11 46) 0 30 27 14 5 (d) 0 27 24 8 43 (e) 7 24 18 1o 52 (h) 11 14 20 9 TABLE 5 Continued Rate of inhibition Compound (I) No. Compound (lV) Transplanted rice Echinochloa Eleocharis Cyperus Potamogeton No. or (V) No. i

(i') 0 5 l6 0 39 (14) (d) 2 100 100 54 98 (14) (h) 8 100 I00 60 79 (d) 0 100 100 77 97 17) (d) 0 94 100 52 67 17) (h) 7 90 100 66 18) (d) 0 100 100 7l 84 (18) (e) 9 100 100 69 89 18 (h) 7 X00 100 58 90 (19) (d) 0 100 100 68 85 (23) (d) 0 100 100 79 (23) (h) 11 100 100 53 81 (35) (h) 17 100 100 55 (35) (d) 8 100 100 63 69 (46) (e) 0 100 100 66 88 (46) (h) 3 I00 I00 65 73 (14) (h') 7 100 100 56 60 14 (i') 0 100 100 58 84 (15) (i') 0 100 100 S2 86 13) (g') 0 100 100 64 (18) (i') 0 100 100 59 (19) (i') 0 I00 55 85 23 0 100 100 60 88 35 (i') 0 100 100 60 83 46 (i') 0 100 100 60 85 EXPERIMENT 6 l/5,000-Are Wagners pots were sown with Digitaria adscendens Henr., Portulaca oleracea L., Chenopodium album L. var. centrorubrum Makino, Alopecurus aequalis Sobol. var. amurensis Ohwi. and Stellaria media Cyr., respectively, 50 seeds were covered with soil to 1 cm thick, the pots were irrigated to such a degree that the surface layer of the soil was barely moistened, and were evenly sprayed with the following suspensions at the rate of 2 ml. per pot. Thus 30 percent of each compound of the above mentioned general formula (I), 6

percent of each compound of the general formula (IV) 40 or (V), 5 percent sodium lignosulfonate, 5 percent polyoxyethylene alkylaryleter and 54 percent clay were mixed together and comminuted to prepare a wettable powder. On the other hand, compounds of general formula (I) (lV) and (V), 30 percent, 5 percent, and 6 percent, respectively, were each mixed with 5 percent sodium lignosulfonate, 5 percent polyoxyethylene alkylarylether and the balance of clay, i.e., 60 percent, 84 percent and 84 percent, respectively, and the resulting mixtures were comminuted to prepare wettable powders. Each of those wettable powders was suspended in water at the rate of 25 g. to 10 litres water. One month after the treatment, the top fresh weight of each surviving plant was measured and the rate of inhibition was calculated in the same manner as Experiment 2. The experiment was replicated three times. The experiment on Alopecurus and Stellaria was conducted in early spring and that on the other weeds was carried out in early summer.

Ihe results are set forth in Table 6.

TABLE 6 Rate of inhibition Compound (I) No. Compound (lV) Digitaria Portulaca Chenopodium Alopecurus Stellaria 1 glare No. or (V) No.

glare (2) 47 8 28 44 44 (3) 33 15 17 34 22 (I4) 54 9 35 28 60 50 10 40 27 48 (a) 35 36 52 25 68 (b) 23 22 43 I7 62 (h) l0 l0 3] 2] 46 (d) 37 42 60 41 70 (e) 25 30 53 23 58 (g) 27 36 58 35 60 (h') 24 29 61 20 66 (i') 28 33 53 30 59 (2) (b) 100 I00 100 100 100 (2) (h) 96 100 100 I00 100 (3) (a) 100 100 100 100 100 (14) (a) 100 100 100 100 100 (14) (h) 100 100 100 100 100 (38) (b) 100 100 I00 I00 100 (2) (d') 100 100 100 100 100 (2) (e) 100 100 100 100 100 (2) (i') 100 100 100 100 100 (3) (d) lOO 100 100 100 100 (14) (h') 100 100 lOO 100 100 ([4) (i') 100 100 100 I00 100 (38) (g') 100 100 100 100 I00 TABLE 7 Monochorla Fresh Number OI weight surviving Cyperus Llndernia Dry Number of Dry Number of weight surviving weight surviving (gJpot) plant (gJpot) Oruzn action Echinochloa Fresh Number of weight surviving stem (gJpot) weight (e-lpot) Dos- Height Number of (cm) plant plant plant (gJpot) Drug or cggcgoo: o 5 Pic 6 d MOMMOODQDO ,aILBRY-Hiii an11565551551555Berni-1 5aim:"

EXPERIMENT 7 Concrete pots, 60 by 60 cm installed outdoors, were filled with paddy-field soil and then were sown with 50 seeds of Echinochloa crus-galli (L.) Beauv. var. oryzicola Ohwi. Then, Oryza sativa L. (the average height is 16.5 cm and the average number of leaves is 3.9) were transplanted to the above pots, at the rate of 16 plants per pot. And a constant amount of mixture of weeds of Monochoria vaginalis Pres], Cyperus microiria Steudel, Lindernia pyxidaria L., were mix-sown to the above pots. When the average height of Oryza sativa L.

reached 23.4 cm and the average number of the leaves is 6 and when the average height of Echinochloa reached 19.5 cm and the average number of the leaves is 3.8, the granules prepared below were applied to the weeds covered with water at a depth of 5 cm. The granules contained one or more of 7 percent of 2-( 2-chlorobenzylthio)-5-( n-propyl)-1,3,4-oxadiazole, 1.5 percent of 2-methylthio-4,6-bis(ethylamino)-1,3,5- triazine and 1.5 percent of 3 (3-chloro-4- bromophenyl 1 -methyl- 1 -methoxyurea, separately with bentonite making up for the balance in each instance. The same depth of water was kept for a week after applying the granules. A month after the treatment, the plants were weighed alive and the average of each three replicates was taken. The results are shown inlalz e Examples of the invention include:

Example 1 A dust prepared by blending 2 percent of 2- benzylthio-S-methyl-l,3,4-oxadiazole with 98 percent of talc.

Example 2 An emulsifiable solution prepared by mixing 20 percent of 2-(2-chlorobenzylthio)-5-(n-propyl)-1,3,4- oxadiazole, 10 percent of polyoxyethylenealkylarylether and percent of methylnaphthalene.

Example 3 A wettable powder prepared by mixing and comminuting 20 percent of 2-(2-bromobenzylthio)-5-ethyl- 1,3,4-thiadiazole, 4 percent of sodium lignosulfonate, 4 percent of polyoxyethylene alkylarylether and 72 percent of clay.

Example 4 7 Example 5 A granular composition prepared by kneading a mixture of 3 percent of 2-(4-chlorobenzylthio)-5-methyl- 1,3,4-oxadiazole, 0.7 percent of 2-methyl-4-chlorophenoxyacetic ethylester and 96.3 percent of bentonite with water and granulating the resulting mass.

Example 6 A wettable powder prepared by mixing and comminuting 30 percent of 2-(2-chlorobenzylthio)-5-ethyl- 1,3,4-oxadiazole, 6 percent of 3-(3-chloro-4- bromophenyl)-l-methyl-l-methoxyurea, 5 percent of polyoxyethylene alkylarylether and 54 percent of clay.

i 7' Example 7 A granular composition prepared by mixing and granulating percent of 2-(2-chlorobenzylthio)-5- ethyl-1,3,4-oxadiazole, 1.5 percent of 2-methylthio- 4,6-bis(ethylamino)-1,3,5-triazine and 93.5 percent of bentonite.

Example 8 A granular composition prepared by mixing and granulating 5 percent of 2-(4-chlorobenzylthio)-5- ethyl-1,3,4-thiadiazole, 1.5 percent of 2-methylthio- 4,6-bis(ethylamino) 1,3,5-triazine and 93.5 percent of bentonite.

Example 9 What is claimed is:

1. A herbicidal composition which comprises, as the active ingredient, a herbicidally effective amount of (A) a compound of the formula wherein R is hydrogen or alkyl of one to nine carbon atoms, X is oxygen or sulfur, Y is halogen, lower alkyl, lower alkoxy or nitro, and k is zero or an integer from 1 to 5 and (B) a compound of the formula wherein Y is chlorine or lower alkylthio, R is lower alkyl, and R is azido or lower alkylamino, the ratio of AB being l.0:0.ll.0.

2. A herbicidal composition claimed in claim 1, wherein the compound of formula (I) is 2-(2- chlorobenzylthio)-5-(n-propyl)-l ,3,4-oxadiazole and the compound of formula (IV) is 2-methylthio-4,6- bis(ethylamino)-1,3,5-triazine.

3. A herbicidal composition claimed in claim 1, wherein the compound of formula (I) is 2-(2- chlorobenzylthio)-5-ethyl-l,3,4-oxadiazole and the compound of formula (IV) is 2-methylthio-4,6-bis(ethylamino)- 1 ,3 ,S-tn'azine.

4. A method for destroying dicotyledonous and monocotyledonous weeds which comprises applying to an area infested with such weeds or weed seeds 21 composition according to claim 1. 

2. A herbicidal composition claimed in claim 1, wherein the compound of formula (I) is 2-(2-chlorobenzylthio)-5-(n-propyl)-1, 3,4-oxadiazole and the compound of formula (IV) is 2-methylthio-4,6-bis(ethylamino)-1,3,5-triazine.
 3. A herbicidal composition claimed in claim 1, wherein the compound of formula (I) is 2-(2-chlorobenzylthio)-5-ethyl-1,3,4-oxadiazole and the compound of formula (IV) is 2-methylthio-4,6-bis(ethylamino)-1,3,5-triazine.
 4. A method for destroying dicotyledonous and monocotyledonous weeds which comprises applying to an area infested with such weeds or weed seeds a composition according to claim
 1. 